Late transition metal catalysts for the co- and terpolymerization of olefin and alkyne monomers with carbon monoxide

ABSTRACT

A catalyst and method for the co-and terpolymerization of monomers of ethylene, other olefins, and alkynes with carbon monoxide is provided. Such a catalyst a method can be used for form living polymers. The catalyst of the present invention comprises an active cationic portion of the formula ##STR1## wherein M is a Group VIII metal, L 1  and L 2  are two electron donor ligands or are joined to form a bidentate four electron donor ligand, R is alkyl, aryl or acyl, and L 3  is CO or a ligand capable of being displaced by CO; and a non-coordinating anionic portion, soluble in inert solvents of the formula 
     
         X.sub.n G.sup.- 
    
     wherein G is B, CH, N, SO 3 , SO 3  CH, R f  SO 2  CH, or NSO 2  R f  wherein R f  is C n  F 2+1  where n is 1 to 10 and X is F,R f  SO 2 , FSO 2  or C 6  H.sub.(5-m) Z m  wherein Z is F, C1, a hydrocarbyl radical, substituted hydrocarbyl radical or combinations thereof, and m is from 1 to 5, and n of X n  is from 1 to 4.

This application is a continuation of U.S. application Ser. No.07/827,681, filed 29 Jan. 1992, now abandoned, which is acontinuation-in-part of U.S. application Ser. No. 07/513,241, filed 20Apr. 1990, now abandoned.

BACKGROUND OF THE INVENTION

The present invention relates to the co- and terpolymerization ofmonomers of ethylene, other olefins, and alkynes and mixtures thereof,with carbon monoxide, and more particularly to a polymerization catalystfor the same.

It is well known that ethylene and 1-olefins can be polymerized with aZiegler-type catalyst derived from a transition metal halide and analuminum alkyl. Ziegler-type catalysts, however, are rare when thetransition metal is a late transition metal, such as a Group VIII metal.Also, aluminum alkyl is a pyrophoric liquid and hazardous to use.

In addition, in some early transition metal systems having a cationicspecies and an anionic species, there appears to be a reaction betweenthe cationic species and the anionic species which deactivates theactive cationic species, and more particularly the catalyst. Thus,attempts have been made to stabilize the active cationic species with adifferent anionic species. For example, it has been proposed in U.S.Pat. Nos. 4,791,180 to Turner and 4,794,096 to Ewen to use excessamounts of alumoxane with various active cationic Ziegler-typecatalysts. These catalysts, however, typically require an undesirableexcess of the alumoxane (i.e., greater than about 1:1000 weight ratio ofcatalyst to alumoxane). Moreover, these catalysts are highly subject topoisoning with basic impurities.

It has also been proposed in EPO Patent Nos. 0,277,003 and 0,227,004,both to Turner, to use an anionic species comprising a plurality ofboron atoms to stabilize active cationic species based on zirconium,titanium or hafnium. However, the types of monomers and solvents whichmay be used with cationic species based on early transition metals islimited because of the incompatibility of these metals with monomers andsolvents bearing functional groups.

Various catalysts to copolymerize carbon monoxide and olefins have beenproposed. For example, a catalyst to copolymerize carbon monoxide and atleast one olefinically unsaturated hydrocarbon has been proposed in U.S.Pat. Nos. 4,788,279 and 4,786,714, both to Drent. The catalyst isobtained by the reaction of a Group VIII metal compound with a nitrogenbidentate ligand, an anion of a non-hydrohalogenic acid having a pKa ofless than 6 (e.g., sulfuric acid, perchloric acid, sulfonic acids andcarboxylic acids), with or without an organic oxidant. However, polymersformed using such catalysts tend to have a wide and variable molecularweight distribution thus reducing the potential commercial utilitythereof. Moreover, such catalysts tend to require more severe reactionconditions, e.g., high pressure and high temperatures.

Thus, it would be highly desirable to provide a catalyst for the co- andterpolymerization of monomers of ethylene, other olefins, and alkyneswith carbon monoxide which is stable at a wide variety of temperatures,is resistant to impurities, is not hazardous to make and use, and iscapable of being used with a wide variety of monomers and solventsincluding those with functional groups. It would also be desirable toprovide a catalyst which provides a controlled molecular weight and anarrow molecular weight distribution of the polymer formed during theco- or terpolymerization process. Such a controlled molecular weight andnarrow molecular weight distribution facilitates the tailoring ofpolymer properties such as melting point, glass transition temperature,crystallinity, etc.

SUMMARY

To this end, a catalyst and a method of co- and terpolymerizing monomersof ethylene, other olefins, and alkynes with carbon monoxide areprovided by the present invention. In particular, the catalyst of thepresent invention comprises an active cationic portion of the formula##STR2## wherein M is a Group VIII metal, L¹ and L² are two electrondonor ligands or are joined to form a bidentate four electron donorligand, R is alkyl, aryl or acyl, and L³ is CO or a ligand capable ofbeing displaced by CO; and a non-coordinating anionic portion of theformula

    X.sub.n G.sup.-

wherein G is B, CH, N, SO₃, R_(f) SO₂ CH, or NSO₂ R_(f) wherein R_(f) isC_(n) F_(2n+1) where n is 1 to 10, and X is F, R_(f) SO₂, FSO₂ or C₆H.sub.(5-m) Z_(m) wherein Z is F, Cl, a hydrocarbyl radical, substitutedhydrocarbyl radical or combinations thereof, and m is from 1 to 5, and nof X_(n) is from 1 to 4.

The present invention also includes the polymerizable mixture comprisingthe monomers of ethylene, other olefins and alkynes, carbon monoxide andthe catalyst described above.

Co- and terpolymerization can be accomplished by contacting a monomer ofethylene, other olefins or alkynes and carbon monoxide with thecatalyst. The present invention can be used to form a living polymer ofcarbon monoxide and the various olefins and alkynes. The term "livingpolymer" relates herein to a polymerization system wherein the catalystis part of the polymer chain, and its activity remains even afterpolymerization has ended. Such a system can be used to produce polymerscharacterized by a controlled molecular weight and a narrow molecularweight distribution. Additionally, block copolymers can be formed bycontrolling the amount of the olefin monomers added. For example, a[A--CO]_(n) [B--CO]_(m) block copolymer can be formed by firstcatalyzing the co-polymerization of alkene B and carbon monoxide, andwhen alkene B has been consumed adding a predetermined amount of alkeneA.

In one embodiment, the catalyst comprises an active cationic portion ofthe formula ##STR3## wherein M is palladium or nickel, L¹ and L² are twoelectron donor ligands or are joined to form a bidentate four electrondonor ligand, R is alkyl, aryl or acyl, and L³ is CO or a ligand capableof being displaced by CO; and a non-coordinating anionic portion of theformula ##STR4## wherein X is F, Cl, hydrocarbyl radical, substitutedhydrocarbyl radical, or combinations thereof, and n is from 1 to 5.

In another embodiment, the catalyst comprises an active cationic portionof the formula ##STR5## wherein M is palladium or nickel, L¹ and L² are2-electron donor ligands or are joined to form a single 4-electron donorligand, R² and R³ are methylene units (--CH₂ --) or substitutedmethylene units, and R⁴ is an alkyl or aryl group, and a stabilizing,non-coordinating anionic portion of the formula ##STR6## wherein X is F,Cl, a hydrocarbyl radical, substituted hydrocarbyl radical, orcombinations thereof, and n is from 1 to 5.

DETAILED DESCRIPTION OF THE INVENTION

The present invention is directed to a catalyst for the co- andterpolymerization of monomers of ethylene, other olefins, or alkynes,with carbon monoxide. The catalyst includes an active cationic portionand an anionic portion which is soluble in a wide range of solvents.

The active cationic portion can have the formula ##STR7## M is a latetransition metal, and namely a Group VIII metal selected from the groupconsisting of iron, cobalt, nickel, ruthenium, rhodium, palladium,osmium, iridium and platinum. Preferred are palladium, platinum andnickel.

L¹ and L² are two electron donor ligands or are joined to form abidentate four electron donor ligand. The ligands have center atomsbearing non-bonded electron pairs such as atoms of N, P, S and O andbearing H, alkyl, aryl and other groups which render L¹ and L²electronically neutral. For example, L¹ and L² can be a phosphine, e.g.,PR'₃ wherein R' is a hydrocarbyl radical or a substituted hydrocarbylradical, P(OR")₃ wherein R" is a hydrocarbyl radical or a substitutedhydrocarbyl radical, or PX'₃ wherein X' is fluorine or chlorine; and Ris H, a hydrocarbyl radical or a substituted hydrocarbyl radical asabove.

L¹ and L² can be joined to form a bidentate four electron donor ligandby a bridging group selected from the group consisting of alkyl and arylgroups and substituted examples thereof. Specific examples include, butare not limited to, 2,2'-bipyridine, 1,10-phenanthroline,1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane,1,2-bis(dimethylphosphino)ethane and bis(dimethylphosphino)methane.

R is alkyl, aryl or acyl, for example, and includes, but is not limitedto, CH₃, COCH₃, C₆ H₅ CO and CH₃ COCH₂ CHφCO

L³ is CO or a ligand capable of being displaced by CO. Exemplary ligandsinclude but are not limited to H₂ O, RCN and ROH wherein R is alkyl oraryl, C₆ H₅ Cl, CH₂ Cl₂, ketones (e.g., acetone), ethers (e.g., diethylether or tetrahydrofuran), and amines.

The cationic portion can also have the formula ##STR8## M is preferablypalladium or nickel, L¹ and L² are as defined previously, R² and R³ aremethylene or substituted methylene units, and R⁴ is an alkyl or arylgroup.

The stabilizing anionic portion is non-coordinating and soluble in awide variety of solvents. The anionic portion can have the formula

    X.sub.n G.sup.-

wherein G is B, CH, N, SO₃, SO₃ CH, R_(f) SO₂ CH, or NSO₂ R_(f) whereinR_(f) is C_(n) F₂₊₁ where n is 1 to 10 and X is F, R_(f) SO₂, FSO₂ or C₆H.sub.(5-m)Z_(m) wherein Z is F, Cl, a hydrocarbyl radical, substitutedhydrocarbyl radical or combinations thereof, and m is from 1 to 5, and nof X_(n) is from 1 to 4. Specific examples include but are not limitedto (CF₃ SO₂)₂ CH, (CF₃ SO₂)₂ N and CH₃ C₆ H₄ SO₃. A preferred anionicportion is ##STR9## wherein X is F, Cl, hydrocarbyl radical, substitutedhydrocarbyl radical, or combinations thereof, and n is from 1 to 5. Apreferred anionic portion of this formula istetrakis[3,5-bis(trifluoromethyl)phenyl] borate (i.e., X is CF₃ and n is2).

The catalyst is prepared in a variety of ways, using techniques andprecursors of the cationic and anionic portions commonly known to thoseskilled in the art. One method is to add the cationic portion precursorto a reaction vessel containing an appropriate solvent. The solventshould be able to dissolve the catalyst species, should be liquid attemperatures at which polymerization reactions are conducted, and thecatalyst should be stable in the solvent. Suitable solvents are, forexample, methylene chloride, benzene, toluene, chlorobenzene, methanol,diethyl ether and the like. The anionic portion precursor is then addedto the reaction vessel. Usually, the anionic portion precursor is in itsacid form. The acid form can be prepared by adding 1 equivalent of HClto the sodium salt of the anionic portion precursor in diethyl ether.Typically, the ratio of cationic portion precursor to anionic portionprecursor is 1:1.05. Preferably, the reaction is completed under dry,oxygen-free conditions using solvents dried under nitrogen bydistillation from either Na/benzophenone or P₂ O₅. It is usuallypreferred that the anionic portion precursor is added to the cationicportion precursor rather than in the reverse order.

The catalyst can be prepared directly in the solvent used forpolymerization, as in the example described above, or the catalyst canbe isolated free of solvent and stored in this state. In thisapplication, the cationic portion precursor is dissolved in a solventwhich is a weakly complexing material, such as acetonitrile, and istreated with a small excess of the acid form of the anionic portionprecursor, also dissolved in acetonitrile or other solvent. Afteraddition has been completed, excess solvent is removed at reducedpressure. The catalyst prepared in this way is dissolved in thepolymerization solvent of choice just prior to its use.

The catalysts of the present invention are particularly useful in theco- and terpolymerization of carbon monoxide and monomers of ethylene;α-olefins such as propylene, 1-butene, 1-hexene and 1-octene;norbornylene, styrene and substitute styrenes, diolefins such asbutadiene, 1,4-hexadiene, 1,5-hexadiene and 1,3-pentadiene; olefinshaving functional groups such as halides, esters, ethers, ketones,aldehydes, fluoroalkyls and aryls; and alkynes such as acetylene; andmixtures thereof.

The resulting co- and terpolymers have utility in a wide variety ofpolymer systems. For example, the co- and terpolymers can be used tofacilitate the blending of other polymers (i.e., can be used ascompatiblizers). The co- and terpolymers can be used in systemsrequiring a photodegradable polymer such as in thermoresist applicationsor for materials that photodegrade over an extended period. The co- andterpolymers can be used in systems requiring a high T_(g) such as inhigh performance polymers. They can be used in systems requiring highcrystallinity such as in high impact polymers.

In a preferred embodiment, the catalyst and method of the presentinvention can be used to form a living polymer of carbon monoxide andthe various olefins and alkynes. The catalyst is part of the polymerchain, and its activity remains after polymerization has ended. Such asystem can be used to produce polymers characterized by a controlledmolecular weight and a narrow molecular weight distribution. Themolecular weight distribution is typically defined as the polydispersitywherein ##EQU1## This value is approximately equal to 1+(1/p) wherein pis the degree of polymerization. The value of the polydispersity willapproach one as the degree of polymerization increases such as when apolymer system has a narrow molecular weight distribution indicative ofliving polymers. Thus, for example, polyketones (e.g., copolymer of4-t-butylstyrene and carbon monoxide) can be formed having a narrowmolecular weight distribution, namely a polydispersity ranging fromabout 1.03 to about 1.40.

The catalyst and method of the present invention can be used to formblock copolymers by first catalyzing the co-polymerization of alkene Band carbon monoxide, and when alkene B has been consumed adding apredetermined amount of alkene A to form a copolymer having the generalformula [A--CO]_(n) [B--CO]_(m).

Polymerizations are conducted by solution, slurry or gas phase processesat temperatures in approximately the range -20° C. to 150° C., underatmospheric, super-atmospheric or sub-atmospheric pressures of carbonmonoxide (or other gases when the alkene is gaseous at the particularreaction temperature), and for periods of time ranging from 1 minute to1000 hours. A polymerizable mixture is formed comprising the catalyst,the monomers to be co- or terpolymerized, and carbon monoxide. Thesolvent employed as the polymerization medium can be functionalizedalkanes such as methylene chloride or chloroform, an ether such asdiethyl ether, a ketone such as acetone or butanone, an alcohol such asmethanol or ethanol, or an aromatic hydrocarbon such as chlorobenzene.Chlorobenzene and methylene chloride are preferred as the polymerizationmedium. Pigments, anti-oxidants, light stabilizers and other additivesknown to those skilled in the art may be added to the polymer.Polymerization can be controlled by exposure to acid, hydrogen gas orusing other techniques of control commonly known to those skilled in theart.

EXAMPLES

The following examples are provided to further illustrate the inventionand the various embodiments thereof but should not to be construed aslimiting the scope thereof. All preparative manipulations were carriedout using conventional Schlenk techniques, Fisher-Porter reactortechniques, Parr reactor techniques, or combinations of thesetechniques. Materials which were demonstrated to be sensitive to oxygen,as is the case with certain of the nickel precursors, were handled in aVacuum Atmospheres drybox. Dichloromethane was distilled from P₂ O₅ inan atmosphere of N₂, acetonitrile was used as obtained from Burdick &Jackson of Muskegon, Mich. without further purification and withoutexclusion of air, and chlorobenzene was used as supplied by Aldrich Co.of Milwaukee, Wis. Carbon monoxide was used as supplied by Matheson(C.P. Grade), ethylene-CO was used as supplied by Alphagaz (1:1 molarratio of CO to ethylene), and various alkenes were used as obtained fromsuppliers, without further purification.

The polymeric products were isolated in various ways, depending uponphysical properties of the polymer in question. For example, highlycrystalline, highly insoluble materials such as poly(ethylene-CO) andpoly(styrene-CO) were separated from the reaction mixture by suctionfiltration and washed several times with methanol, then dried overnightin high vacuum. Chlorobenzene-soluble polymers such aspoly(4-tert-butylstyrene-CO) were precipitated by pouring thechlorobenzene solution of the polymer into a blender containing methanolor hexane, isolating the solid polymer by suction filtration or bycentrifugation where necessary, and washing the polymer several timeswith methanol and drying overnight in vacuo.

Polymeric products were analyzed by ¹ H NMR and ¹³ C NMR spectroscopy,using appropriate solvents, including CD₂ Cl₂, CDCl₃, and CF₃ COOD, andby infrared spectroscopy. Molecular weights were determined by gelpermeation chromatography. Physical properties such as melting point andglass-transition temperature were determined by thermal gravimetricanalysis/differential scanning calorimetry.

Examples 1-3 describe the preparation of catalysts which are useful inthe process of this invention. In all three cases, co-polymerization ofalkenes with CO were subsequently demonstrated.

Example 1

2,2'-Bipyridinedimethylpalladium (29.2 mg, 0.10 mmol) was dissolved in10.0 mL acetonitrile which had not been freed of O₂, and while thissolution was gently stirred, a solution of 10.0 mL acetonitrile and 110mg (0.11 mmol) diethyloxoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate was added dropwise over a10 minute period. After addition had been completed, the excessacetonitrile was removed at reduced pressure, to provide a quantitativeyield of the catalyst comprising a I-bipy cationic portion and atetrakis[3,5-bis(trifluoromethyl)phenyl]borate anionic portion.##STR10##

The structure of the complexI-bipy/tetrakis[3,5-bis(trifluoromethyl)phenyl]borate was confirmed by ¹H NMR spectroscopy.

Example 2

1,10-Phenanthrolinedimethylpalladium (31.6 mg, 0.10 mmol) was dissolvedin 10.0 mL acetonitrile, and while this solution was stirred with amagnetic stirrer, a solution of 10.0 mL acetonitrile containing 110 mg(0.11 mmol) diethyloxonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate was added over a 10 minuteperiod. After addition had been completed, the excess acetonitrile wasremoved at reduced pressure, to provide a quantitative yield of thecatalyst having a I-phen cationic portion and a tetrakis[3,5-bis(trifluoromethyl)phenyl]borate anionic portion. ##STR11##

The structure of the complexI-phen/tetrakis[3,5-bis(trifluoromethyl)phenyl]borate was confirmed by ¹H NMR spectroscopy, and by elemental analysis.

Example 3

1,2-(diphenylphosphino)ethanedimethylnickel (48.3 mg, 0.10 mmol) wasdissolved in 10.0 mL acetonitrile, and to this stirred solution wasadded, over a 10 minute period, a solution made up of 10.0 mLacetonitrile and 110 mg (0.11 mmol) diethyloxoniumtetrakis[3,5-bis(trifluoromethyl) phenyl]borate. The excess acetonitrilewas removed at reduced pressure to provide the catalyst having aI-diphos cationic portion and atetrakis[3,5-bis(trifluoromethyl)phenyl]borate portion as a glassy,solid residue. ##STR12## The structure of the complexI-diphos/tetrakis[3,5-bis(trifluoromethyl)phenyl]borate was confirmed by¹ H NMR spectroscopy.

Example 4

This example was conducted to determine whether the polymerization is aliving polymer system.

The catalyst was prepared as in Example 2 except the amounts weredoubled. The excess CH₃ CN was removed in vacuo and the catalyst thusproduced was transferred in 80 mL chlorobenzene under N₂ to aFisher-Porter reactor. 4-t-butylstyrene (20 g) was introduced, and theN₂ atmosphere carefully replaced with CO, then the CO pressure wasincreased to 40 lbs. Samples were periodically taken by reducing the gaspressure to just above 1 atm, removing a 2-5 mL sample, andrepressurizing the system to 40 lbs. Except for the earliest samples,which were isolated by removal of all volatile materials by applyinghigh vacuum, polymer samples were isolated by precipitation frommethanol, washing with methanol, and drying in vacuo.

Progress of the reaction was monitored by ¹ H NMR spectroscopy, byintegration of isolated vinyl absorptions of the unreacted styrene andcomparing those values with the ΦCH and two diastereomeric CH₂ protonsof the copolymer, prior to isolation of the polymeric products.

The Table below shows percent conversion of starting styrene to polymer,number-average molecular weight for each polymer sample, weight-averagemolecular weight for each polymer sample, and the calculatedpolydispersity.

    ______________________________________                                                Percent                                                               Sample  Conversion                                                                              MW.sub.n  MW.sub.w                                                                            Polydispersity                              ______________________________________                                        1       7.4       9730      10052 1.03                                        2       19.9      24558     25509 1.04                                        3       27.4      29512     32185 1.09                                        4       39.5      40630     44419 1.09                                        5       45.2      42094     46847 1.11                                        6       48.0      44996     50105 1.11                                        7       52.5      53292     59660 1.20                                        8       61.1      56050     62193 1.11                                        9       62.4      56419     63957 1.13                                        10      84.5      72166     82550 1.14                                        ______________________________________                                    

The reaction was discontinued after 155 hours. The product wasidentified by ¹ H NMR spectroscopy as the polymer with the followingrepeating unit. ##STR13##

A plot of percent conversion vs MW_(n) is linear. This data togetherwith the low polydispersity (e.g., 1.03 to 1.14) indicates that thepolymerization reaction is an example of living polymerization.

Example 5

Example 4 was repeated except that the reaction was terminated afterabout 93 hours. The polydispersity of eleven samples taken throughoutthe experiment showed a low polydispersity range of 1.04 to 1.08indicating living polymerization.

Example 6

The catalyst of Example 2 was redissolved in 40 mL dry chlorobenzene ina 50% ethylene/CO atmosphere. The reaction temperature was variedbetween ambient (25° C.) and 55° C. over the course of the reaction. Thereaction was discontinued after 49 hours although gas absorption wasstill being observed. The solid polymeric material was isolated bysuction filtration, washed several times with CH₂ Cl₂, and dried invacuo to give 1640 mg of a nearly white powder.

Example 7

The catalyst of Example 1 was redissolved in chlorobenzene (40 mL) in aCO atmosphere, and 5 mL styrene (stabilized with 4-t-butyl catechol) wasadded. The reaction was discontinued after 21.5 hours, the solidpolymeric product isolated by centrifugation followed by washing withdiethyl ether, and drying in vacuo. In this way, 2000 mg of light-grey,powdery product was obtained. The ¹ H NMR spectrum (in CF₃ COOD/CD₂ Cl₂)showed the expected alternating ethylene-CO copolymer.

Example 8

The catalyst of Example 2, was dissolved in 40 mL chlorobenzene in anitrogen atmosphere, and the N₂ was carefully replaced with CO byevacuating the system and replenishing the gaseous atmosphere with CO,repeating the process three times. 4-t-butylstyrene (7.0 g, 44 mmol) wasinjected into the stirred solution, and reaction progress was monitoredby measuring CO uptake. After 23 hours of reaction under 1 atm COpressure, the reaction mixture was absorbing 0.5 mL CO/10 minutes. Atthis time, 3.5 g (22 mmol) additional 4-t-butylstyrene was added toessentially double the rate of reaction (i.e., CO uptake was measured at1.1 mL/10 minutes). After 42 hours total reaction time, the reactionmixture was filtered through Celite filter aid, then added towell-stirred methanol (500 mL). The solid obtained in this way wascollected by suction filtration, the residue washed with methanol anddried overnight in high vacuum. The white, powdery solid product weighed6.0 g. Example 8 demonstrates that the reaction is directly dependent onthe concentration of the alkene.

Example 9

Example 8 was repeated except the amount of 4-t-butylstyrene, wasdoubled, as was the solvent volume. During the course of the reaction,samples were removed, polymeric material isolated, and the polymersanalyzed by gel permeation chromatography. Isolation of later fractionswas accomplished by precipitation from methanol; early fractions,because of low molecular weight and high solubility, were isolatedsimply by removal of solvent under high vacuum. In the table below,reaction times, number-average and weight-average molecular weights, andpolydispersity for each sample are shown.

    ______________________________________                                                Reaction                                                              Sample  Time (hrs)                                                                              MW.sub.n  MW.sub.w                                                                            Polydispersity                              ______________________________________                                        1       16        26,544    29,155                                                                              1.10                                        2       24        43,300    49,568                                                                              1.14                                        3       40        53,534    68,188                                                                              1.27                                        4       47        58,358    74,194                                                                              1.27                                        5       64        64,105    82,758                                                                              1.29                                        ______________________________________                                    

The low polydispersity range indicates living polymerization. An IRspectrum obtained on sample 5 showed a carbonyl stretching frequency at1708 cm⁻¹. A differential scanning calorimetry experiment conducted onsample 5 provided a glass transition temperature, T_(g), of 158° C.

Example 10

The catalyst of Example 1 was redissolved in 40 mL chlorobenzene in a COatmosphere, followed immediately by the addition of 10 mL (8.97 g) of97% 4-methylstyrene (the 3% impurity was the 3-methylstyrene isomer).After 23 hours of reaction time, heavy grey precipitate of polymericmaterial was observed, and stirring of the mixture was labored.Additional chlorobenzene (20 mL) was introduced to facilitate stirring.The reaction was discontinued after 25 hours. The reaction was worked upby addition of about 30 mL of methanol, then separating the mixture bycentrifugation, and washing the solid residue with methanol, finallydrying the grayish powdery material in vacuo to yield 7.35 g of product.NMR data (¹ H NMR and ¹³ C NMR spectra) were compatible with theexpected structure of the material.

Example 11

The catalyst of Example 1 was redissolved in 40 mL chlorobenzene in a COatmosphere, followed immediately by the addition of 10 mL of a mixtureof methylstyrenes made up of 67% 3-methylstyrene and 33% 4-methylstyrene(composition assigned on the basis of ¹ H NMR spectrum). In comparisonwith the same reaction involving 4-methylstyrene only the reaction inthe present case was remarkably slower, indicating that 3-methylstyrenedid not react as readily as did the 4-isomer. Furthermore, a precipitatewas not observed; rather, the material formed a gel, after about 23hours, which was not deformed by changes in the direction of lines ofgravity. Additional chlorobenzene (20 mL) was added in order to renderthe mixture more mobile, without useful effect. The reaction wastherefor discontinued. The 6.0 g yield of polymer, isolated afterphysically mixing the gel described above with 30 mL methanol andcollecting by suction filtration, then washing with methanol and dryingin vacuo, was powdery and nearly white in color. The lower yield of thismaterial is compatible with the earlier observation, based on rate ofgas absorption, that 4-isomer of methylstyrene is more reactive than the3-isomer.

Example 12

Double amount of catalyst of Example 1 was dissolved in 80 mLchlorobenzene (degassed) in an atmosphere of 50% ethylene/CO, and thissolution was transferred to a Fisher-Porter apparatus forelevated-pressure reaction. The gas mixture was passed through a BASFcatalyst at 40° C., and through activated 4A molecular sieves, to removeO₂ and H₂ O which may have contaminated the ethylene/CO mixture.Ethylene/CO pressure was increased to 30 psi, and the reaction allowedto proceed with stirring for 23 hours. The product was isolated in theusual way, by suction filtration, methanol washing, and drying in vacuo,to provide 1.61 g of light-grey, granular solid.

Example 13

The catalyst of Example 2 was redissolved in 40 mL chlorobenzene andtransferred to a Fisher-Porter apparatus under 50% ethylene/CO (the gasmixture was purified in the manner described in Example 12. The systemwas pressurized with 50% ethylene/CO to 40 psi, and reaction allowed toproceed at room temperature for 41 hours, at which point it wasdiscontinued. The solid residue was collected by suction filtration,washed with methanol and dried in vacuo, to give 1.41 g of nearly whitepolymer.

Example 14

The reaction was conducted as described in Example 13, with the singleexception that styrene (5.0 mL) was introduced just prior topressurization to 40 psi with 50% ethylene/CO. Reaction was allowed toproceed at room temperature, and the reaction solution became moreviscous as reaction continued. After 26 hours, the reaction mixture wasfiltered to remove traces of dark residue, then the reaction solutionwas poured into 300 mL CH₃ OH in a rapidly-stirred blender. The ropeymaterial which separated was gathered, redissolved in dichloromethane,and reprecipitated from 300 mL CH₃ OH as before. The elastic materialwas dried in vacuo to give a tough, elastic material. The ¹ H NMRspectrum suggested an ethylene/styrene molar ratio of about 1.5:1. Gelpermeation chromatographic analysis of this material showed it to have anumber-average molecular weight of 41,990 and a weight-average molecularweight of 44,036, to give a polydispersity of 1.05.

Example 15

The catalyst of Example 1 was redissolved in 40 mL chlorobenzene in a50% ethylene/CO atmosphere, 5 mL styrene introduced, and the ethylene/COpressure increased to 40 lbs for the reaction's duration. After 45hours, the reaction mixture was poured into about 300 mL CH₃ OH stirredrapidly in a blender. In this way, 4.9 g of a tough, fibrous materialwas obtained.

Gel permeation chromatography of a sample of this material showed anumber-average molecular weight of 44,337, and a weight averagemolecular weight of 51,540, to produce a polydispersity of 1.16indicative of a living polymer.

Example 16

The catalyst employed in this experiment was prepared from 32 mg (0.1mmol) (4,4'-dimethyl-2,2'-bipyridine)palladium(CH₃)₂ and 106 mg(slightly in excess of 0.1 mmol) diethyloxoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate in 20 mL CH₃ CN. Removalof excess acetonitrile in vacuo, and redissolving the residue in 40 mLchlorobenzene in a CO atmosphere, then injecting 5 mL of a 2:1 mixtureof 3-methyl and 4-methylstyrenes and allowing the reaction to proceed atambient temperature and atmospheric pressure resulted in the productionof 5.84 g of a brittle yellowish polymeric product.

Examples 17-22 demonstrate preparing the catalyst in the presence of oneof the monomers to be copolymerized.

Example 17

1,2-(diphenylphosphino)ethanedimethylpalladium (75 mg, 0.14 mmol) wasdissolved in 15 mL dichloromethane (distilled in N₂ atmosphere from P₂O₅), and the solution was saturated with ethylene. This solution wastreated with 15 mL of CH₂ Cl₂ containing 145 mg (0.14 mmol) ofdiethyloxonium tetrakis [3,5-bis(trifluoromethyl)-phenyl]borate,similarly saturated with ethylene. The feed gas was changed to 50%ethylene/CO, and allowed to proceed for 15 hours. Grey polymericmaterial (90 mg), identified as ethylene/CO copolymer, was obtained.

Example 18

2,2'-Bipyridinedimethylpalladium (39 mg, 1.34 mmol) in 10 mLchlorobenzene in a propylene atmosphere was treated with 135 mg (1.33mmol) diethyloxonium tetrakis[3,5-bis(trifluoromethyl)phenyl]borate in10 mL chlorobenzene, also saturated with propylene. Propylene uptake wasmonitored over about 50 minutes; at this point, CO was introduced atabout the same rate as propylene flow. After 2.5 hours, temperature wasincreased from 25° C. to 40° C. Reaction was discontinued after 5 hours,the reaction mixture filtered to remove some dark residue, and thesolvent removed at reduced pressure. A viscous orange oil (210 mg) wasobtained whose ¹ H NMR spectrum showed absorptions between δ3.3 andδ0.8, and whose IR spectrum showed a substantial absorption at 1708 cm⁻¹attributable to aliphatic carbonyl which would be present in theexpected polymeric structure.

Example 19

2,2'-Bipyridinedimethylpalladium (29.2 mg, 0.1 mmol) in 10 mL CH₃ OH(distilled from Mg/I₂ under N₂, then degassed by the freeze-thaw method)was treated with a solution of 10 mL of the same CH₃ OH containing 101mg (0.1 mmol) diethyloxoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate in an ethyleneatmosphere. After it was ascertained that ethylene uptake was occurring,the feed gas was switched to 50% ethylene/CO. Gas uptake was monitoredover a 165 minute period, and the reaction was discontinued at thispoint. The dark grey polymeric material was isolated by filtration,washed with diethyl ether, and dried in vacuo to provide 285 mg of thepolymeric material.

Example 20

The reaction procedure described in Example 19 was followed, except thatdiethyl ether, degassed by freeze-thaw method, was employed as thesolvent. The reaction was continued for 21 hours, at which point thepolymer was collected by suction filtration, washed with diethyl ether,and dried in vacuo to yield 700 mg of a light grey powder.

Example 21

2,2'-Bipyridinedimethylpalladium₂ (29 mg, 0.1 mmol) was dissolved in 10mL CH₂ Cl₂ containing 0.5 mL CH₃ CN (the solvent was carefully degassedby the freeze-thaw method). This solution was treated with 10 mL CH₂ Cl₂containing 101 mg (0.1 mmol) diethyloxoniumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate. After stirring thesolution for about 5 minutes, the solvent was removed at reducedpressure to provide an orange-red glassy solid material. This wasredissolved in 20 mL chlorobenzene in an ethylene atmosphere, and afterthree minutes the atmosphere was replaced with a 50% ethylene/COmixture. Reaction was discontinued after 19 hours, although gasabsorption was still continuing at a reduced rate. The solid product wascollected by suction filtration, then washed with CH₂ Cl₂ and dried invacuo to give 1.12 g of a light-grey powdery material.

Example 22

The reaction described in Example 21 was repeated, except that thesolvent was dichloromethane (CH₂ Cl₂) instead of chlorobenzene. The rateof gas absorption was about the same, and the yield was only slightlylower 1.0 g of a darker grey powdery material.

Example 23

In Example 23, it is demonstrated that the catalyst may be pre-formed inan inert atmosphere such as N₂, stored indefinitely as a glassy solid,and dissolved in chlorobenzene in the atmosphere of the reaction.

The catalyst of Example 1 was redissolved in 20 mL chlorobenzene(degassed by freeze/thaw method) in a 50% ethylene/CO atmosphere. Gasuptake was monitored and was about the same rate as seen in previousexamples. Reaction was discontinued after 20 hours; 1.04 g of alight-grey powdery material was obtained.

Example 24

2,2'-Bipyridinedimethylnickel (24,5 mg, 0.1 mmol) complex was dissolvedin 10 mL degassed CH₃ CN, and 101 mg (0.1 mmol) of diethyloxoniumtetrakis[3,5-bis (trifluoromethyl)phenyl]borate in 10 mL CH₃ CN wasadded. After addition was complete, excess acetonitrile was removed invacuo to produce a bright yellow, glassy material which began tocrystallize. This material was redissolved in degassed CH₂ Cl₂ (20 mL)in a 50% CO/ethylene atmosphere. The reaction was discontinued after 5hours, since gas absorption had almost ceased. The solid residue whichhad formed was collected by suction filtration, washed with methylenechloride, and dried in vacuo to provide 142 mg of a pale greenish solid.The IR spectrum of this material showed a carbonyl absorption expectedfor the ethylene/CO copolymer.

Example 25

The catalyst of Example 2 was redissolved in 80 mL chlorobenzene, thesolution was transferred to a Fisher-Porter apparatus, and 20 mL styrenewas added. The solution was cooled in an ice bath, and propylene wasintroduced until a definite volume change was noted. The Fisher-Porterapparatus was closed and pressurized to 40 lbs with CO.

After 20 hours, the reaction mixture was cooled to 0° C., and morepropylene was introduced in the manner described previously. The systemwas repressurized to 40 lbs, and allowed to react for an additional 24hours, then discontinued. Polymeric product was precipitated by additionof the reaction mixture to rapidly stirred methanol. After drying invacuo, 7.0 g of a granular, off-white solid was obtained. ¹ H NMRspectra suggest a styrene-propylene ratio of about 3 to 1.

Example 26

The catalyst of this example was prepared from 36.1 mg (0.1 mmol)[5-nitro-1,10-phenanthroline]dimethylpalladium and 106 mg ofdiethyloxonium tetrakis[3,5-bis(trifluoromethyl)Phenyl]borate, in 20 mLCH₃ CN. Evaporation of excess acetonitrile at reduced pressure produceda brownish, glassy residue which was redissolved in 40 mL chlorobenzeneunder CO atmosphere, and treated with 5 mL 4-t-butylstyrene. Thereaction was allowed to proceed for 48 hours. Workup of the reactionmixture involved pouring into rapidly stirred methanol, filtration ofthe precipitate, and drying in vacuo, to give 3.12 g of copolymer.

In a control reaction which was run alongside the5-nitro-1,10-phenanthroline dimethylpalladium catalyzedcopolymerization, in order to ascertain the effect of the --NO₂ group,1,10-phenanthrolinedimethylpalladium was used. No other modificationswere made. From this control reaction, 2.83 g of copolymer was obtained.Thus the reactions took place at about the same rate, and the effect ofthe --NO₂ group in the bidentate ligand is not large.

Example 27

The catalyst of Example 2 was transferred to a Fisher-Porter apparatusin 40 mL chlorobenzene under CO atmosphere, 20 g norbornylene in 20 mLchlorobenzene was added, the CO pressure was increased to 40 lbs, andthe temperature of the system was raised to 50° C. for one hour, then to60° C. for the remainder of the reaction. The reaction was discontinuedafter 95 hours; the reaction mixture was filtered to remove a smallamount of black residue, and the polymer precipitated by pouring into300 mL well-stirred methanol. The white solid was collected bycentrifugation, washed with methanol, and dried in vacuo to yield 6.6 gof a white powder, soluble in chloroform and dichloromethane, whose ¹ HNMR spectrum was compatible with the expected structure for the product.

Example 28

[2,2'-Bipyridine)methylpalladium(CH₃ CN)]+[(CF₃ SO₂)₂ CH]⁻ was preparedfrom 29.2 mg (0.1 mmol) 2,2'-bipyridinedimethylpalladium and 30 mg (CF₃SO₂)₂ CH₂ in 20 mL CH₃ CN, then removing the excess CH₃ CN byevaporation in vacuo. This material was redissolved in 40 mLchlorobenzene in a CO atmosphere, followed by addition of 10 mL of a 3:1mixture of 3-methylstyrene and 4-methylstyrene. Reaction wasdiscontinued after 21 hours, at which point the reaction mixture was avery viscous, gel-like material. This was transferred to rapidly stirredmethanol (500 mL), and the precipitate thus produced collected bysuction filtration. After drying the solid product in high vacuum, thegrayish powdery solid weighed 3.0 g.

Example 29

This example demonstrates the synthesis and application of the catalyst[2,2'-Bipyridinedimethylpalladium (CH₃ CN)]tetrakis[3,5-bis(trifluoromethyl)phenyl]borate generated without the useof the acid diethyloxonium tetrakis[3,5-bis(trifluoromethyl)phenylborate].

2,2'-Bipyridinedimethylpalladium (58.4 mg, 0.2 mmol) was dissolved in 20mL degassed CH₂ Cl₂, and the solution was cooled to 0° C. in an icebath. Then 32 mg Br₂ (0.2 mmol) in CH₂ Cl₂ was introduced slowly. Afteraddition was complete, the solution was stirred at 0° C. for two hours,and the solvent was removed at reduced pressure at 0° C. After allsolvent had been removed, the product was a microcrystalline,earth-yellow solid.

The material was redissolved in 30 mL degassed CH₂ Cl₂, and a solutionof 220 mg (8% excess) of sodiumtetrakis[3,5-bis(trifluoromethyl)phenyl]borate in 10 mL CH₂ Cl₂,containing 100 mg CH₃ CN, was introduced at once at room temperature.After three hours, the mixture was filtered to remove separated solid,and the solvent was evaporated to provide a yellow, pasty solid.

This material was redissolved in 40 mL chlorobenzene in an atmosphere ofCO, 10 mL styrene was added, and the reaction allowed to proceed (in COatmosphere) for 24 hours. Workup by centrifugation, and washing of thesolid thus collected with methanol followed by drying in vacuo, provided4.1 g of grey polymeric material.

That which is claimed is:
 1. A polymerization catalyst for the co- andterpolymerization of monomers of ethylene, other olefins and alkyneswith carbon monoxide said catalyst comprising an active cationic portionof the formula ##STR14## wherein M is palladium or nickel; L¹ and L² aretwo electron donor ligands or are joined to form a bidentate fourelectron donor ligand,R is alkyl, aryl, or acyl, and L³ is CO or aligand capable of being displaced by CO; anda non-coordinating anionicportion of the formula ##STR15## wherein X is F, Cl, hydrocarbylradical, halo substituted hydrocarbyl radical, or combinations thereof,and n is from 1 to
 5. 2. A polymerization catalyst according to claim 1wherein said L¹ and L² are covalently joined by a bridging groupselected from the group consisting of alkyl and aryl.
 3. Apolymerization catalyst according to claim 1, wherein the bidentate4-electron donating ligand is selected from the group consisting of2,2'-bipyridine and 1,10-phenanthroline.
 4. A polymerization catalystfor the co- and terpolymerization of ethylene, other olefins and alkyneswith carbon monoxide, said catalyst comprising an active cationicportion of the formula ##STR16## wherein M is palladium or nickel; L¹and L² are two-electron donor ligands or are joined to form a bidentatefour-electron donor ligand;R is alkyl, aryl or acyl, and L³ is CO or aligand capable of being displaced by CO which is selected from the groupconsisting of H₂ O, CH₃ CN, CH₃ CH₂ CN, CH₃ OH, C₆ H₅ Cl, (CH₃ CH₂)₂ O,and CH₂ Cl₂ ; anda non-coordinating anionic portion of the formula##STR17## wherein X is F, Cl, hydrocarbyl radical, halo substitutedhydrocarbyl radical or combinations thereof, and n is from 1 to
 5. 5. Apolymerization catalyst for the co- and terpolymerization of ethylene,other olefins and alkynes with carbon monoxide, said catalyst comprisingan active cationic portion of the formula ##STR18## wherein M ispalladium or nickel; L¹ and L² are two-electron donor ligands or arejoined to form a bidentate four-electron donor ligand;R² and R³ aremethylene units; and R⁴ is alkyl or aryl; anda stabilizing,non-coordinating anionic portion of the formula ##STR19## wherein X isF, Cl, hydrocarbyl radical, halo substituted hydrocarbyl radical orcombinations thereof, and n is from 1 to
 5. 6. A polymerization catalystaccording to claim 5, wherein L¹ and L² are covalently joined by abridging group selected from the group consisting of alkyl and aryl. 7.A polymerization catalyst according to claim 5, wherein said bidentatefour-electron donor ligand is selected from the group consisting of2,2-bipyridine and 1,10-phenanthroline.